Methods and apparatus for improved gasification of carbonaceous feedstock

ABSTRACT

The inventive technology includes methods and apparatus for the generation and application of segregated catalytic additives for the pre-combustion treatment of carbonaceous fuel and/or feedstocks. The application of such segregated additives results in the reduction of environmentally harmful emissions during combustion as well as gasification processes. Specifically, pre-combustion treatment of carbonaceous materials with the inventive additives results in the reduction of NOx and/or mercury emissions by least 20% and 40% respectively.

This application is a continuation application which claims the benefitof and priority to U.S. application Ser. No. 16/238,411, filed Jan. 2,2019; which is a continuation of U.S. application Ser. No. 15/633,635,filed Jun. 26, 2017 and issued as U.S. Pat. No. 10,202,558 on Feb. 12,2019; which is a continuation of U.S. application Ser. No. 14/611,000,filed Jan. 30, 2015 and issued as U.S. Pat. No. 9,688,935 on Jun. 27,2017; which is a continuation of U.S. application Ser. No. 14/177,114,filed Feb. 10, 2014 and issued as U.S. Pat. No. 8,945,247 on Feb. 3,2015; which claims the benefit of and priority to U.S. provisionalapplication No. 61/762,560 filed Feb. 8, 2013. The entirety of each ofthe above-mentioned applications are hereby incorporated herein byreference.

TECHNICAL FIELD

The inventive technology generally relates to the reduction of undesiredemissions of harmful environmental chemical pollutants generated fromthe combustion and/or gasification of carbonaceous fuels and/or otherfeedstocks. The present invention in its various embodiments may includean improved system for the treatment of carbonaceous fuels and/or otherfeedstocks, such as coal, petroleum coke, biomass, petroleum, peat,residual oils and natural gas and the like. Such carbonaceous fuelsand/or other feedstocks may be in liquid, solid or gas form. While avariety of carbonaceous fuels and/or other feedstocks are contemplatedwithin the scope of the invention, reference to any specific fuel sourceis merely exemplary and in no way limiting.

As discussed herein, the inventive technology may provide for a moreefficient combustion, and/or chemical interactions/reactions during thecombustion and/or gasification process thereby causing a reduction ofharmful chemical emissions from carbonaceous and/or other feedstockbased facilities. More generally, the inventive technology may providefor techniques, systems, methods and apparatus that may include apre-treatment of carbonaceous fuels and/or other feedstocks resulting ina reduction in the environmental release of harmful byproducts of theiruse, for example through combustion, pyrolysis and/or gasification andthe like. The invention may be configured for use in combustionprocesses, such as coal combustion facilities as well as non-combustionprocesses such as gasification and/or pyrolysis.

Additional embodiments may specifically include processes that utilizecombustion as well as non-combustion based systems such as gasificationand the like. The invention may also be especially configured forapplication to pulverized coal furnaces/boiler, fluidized bed or cycloneboilers as well as liquid gas combustion systems and other carbonaceousfuel feedstock consumption or reformation systems such as in variousgasification systems. The present invention may in some embodimentsreduce, for example nitrogen oxides (NOx) (including, but not limited toNO, NO2, N2O as well as nitrite and nitrate compounds), and mercuryspecies (Hg) (including, but not limited to elemental HG, Hg vapor, andoxidized Hg vapor and any other mercury containing compound) by at least20% and 40% respectively. In addition, the invention may further reducevarious sulfur oxides (SOx) (including, but not limited to SO, SO₂, SO₃,S₇O₂, S₆O₂, S₂O₂, sulfide and sulfate compounds as well as elementalsulfur) and other combustion and/or gasification emission byproducts ina manner that meets environmental threshold requirements.

In one specific embodiment, the inventive technology may include amethod of generating a catalytically enhanced low emission carbonaceousfuel that produces less harmful environmental pollutants duringcombustion compared to non-treated carbonaceous materials. The processesdisclosed herein being equally applicable to liquid carbonaceousmaterial, solid carbonaceous material, and/or gas carbonaceous material.Additional aspects of the inventive technology may include the methodsand apparatus for the improve yields of, and/or rate of carbonaceousfuel and/or feedstock consumption. Certain embodiments may include,methods of generating a low emission carbonaceous fuel additive that maybe used, for example in the pre-combustion treatment of coal and thelike. In still further embodiments, such carbonaceous fuel additive maybe applied in situ at a point of production, such as a mine, duringtransport, storage or along multiple points of pre-combustionprocessing. Finally, embodiments of the invention may include methods ofcatalyzing the gasification of carbonaceous feedstock that increaseselect product gas components, as well as perhaps reduce harmfulenvironmental pollutants generated during the gasification process.

BACKGROUND OF THE INVENTION

Enormous industrial and technical efforts have been exhausted withvarying degrees of success grappling with the problem of environmentalpollution generated from the processing of carbonaceous material. Forexample, the combustion of coal has provided the backbone of industrialand energy since the start of the industrial revolution. It is estimatedthat the world currently consumes over 4050 MT of coal per year. Suchcoal is utilized by a variety of sectors including: power generation;iron and steel production; cement manufacturing; and as a liquid fuel.For example, it is currently estimated that approximately 45% of all USelectrical production is derived from coal combustion, while coal-firedpower plants generate approximately 40-50% of global electricity. Insome countries, coal generates an even higher percentage of electricity.For example, China produces approximately 80% of its electrical outputfrom coal combustion, while South Africa generates over 90% of its totalelectricity from coal.

Despite renewed emphasis on alternative energy sources, with theexistence of significant coal resources around the world capable ofmeeting large portions of the world's energy needs into the next twocenturies, coal remains and will continue to be a core energy source.However, despite its prevalence, there exist various environmental andregulatory concerns, specifically related to the emission of harmful andunwanted chemical compounds generated from the combustion process. Apartfrom being one of the largest worldwide anthropogenic sources of carbondioxide, coal combustion is a significant source of NOx, SOx andelemental as well as oxidized Hg and other heavy metals. (As describedhereafter, carbonaceous material emissions may also be generallyreferred to as “Carbon Combustion by-Product's” (CCB's).) Such CCBemissions generally require remediation steps to prevent their releaseinto the atmosphere upon combustion. For example, the emissions of SOxand NOx from U.S. power plants are regulated as part of Title IV of theClean Air Act Amendments of 1990 (CAAA). (It should be noted that thepurpose of this application, the term NOx generally encompasses allreactive compounds and/or gases which contain nitrogen and oxygen invarying amounts, such as nitrogen oxides. The term SOx generallyencompasses all reactive compounds and/or gases which contain sulfur andoxygen in varying amounts, such as sulfur oxides. However, the terms NOxand SOX may also encompass any nitrogen or sulfur containing emissiongenerated during the combustion, gasification or other processing methodof carbonaceous materials respectively.)

As detailed below, such traditional systems are limited in theireffectiveness as well as cost. Clearly an inexpensive, comprehensivesolution to the aforementioned problems would represent a significantleap forward in the industry. One area of development is the use ofadditives that may facilitate non-formation and/or removal of emissionsresulting from the consumption of carbonaceous and/or feedstock basedprocesses as discussed above. By way of example, several U.S. patentshave been issued relating to coal combustion byproduct removal. However,the present invention overcomes many of the operational and costdisadvantages associated with current processes involving pre-combustionadditives. For example, past efforts to develop pre-combustion additivesto coal, such as U.S. Pat. Nos. 7,988,939, 7,758,827 (Comrie references)and Zhao Yi, et al. reference each hereby incorporated by referenceherein, have not afforded the various advantages and other combinationsof features as presented herein. Indeed, in the prior art systems,disadvantages often exist that can create problems in a variety ofareas.

For example, the Comrie references teach halogen based sorbents for coalcombustion to facilitate Hg removal from the flue gas; however, suchreferences rely on the addition of halogenated compounds, such ascalcium-bromides to coal prior to combustion. Apart from beingexpensive, such halogenated compounds are also hazardous chemicalsmaking their transport, use and disposal of limited desirability withinthe industry. Such, halogenated compounds further generally requireadditional remediation and disposal steps creating additional undesiredcost and liabilities. For example, none of the Comrie references teachthe use of segregated particulate matter, such as fly ash, and/orsegregated calcium source compounds, such as limestone to achieve thesynergistic catalytic removal or prevention of nitrogen, sulfur and Hgemissions resulting from coal combustion. In addition, the Comriereferences are not applicable to other carbonaceous and/or feedstockbased processes, such as gasification and the like. The use of thesecompounds may also cause slagging, fouling or corrosion of boiler tubesin a combustion furnace.

In another limited example, the Zhao Yi, et al. reference is alsolimiting as it uses lime as a sorbent to effectuate desulfurization anddenitrification. However, use of hydrated lime as an additive ispractically and commercially limited. Apart from the obvious undesirablecaustic chemical profile of using such hydrated lime species, such ascalcium hydroxide, such calcium sources are generally more expensivefurther limiting their usefulness. In addition, the Zhao Yi, et al.reference fails to provide optimal surface area understanding to anypre-combustion additives as well as their addition to a combustible fuelsource reducing their actual effectiveness and preventing somefunctioning. Again, the Zhao Yi, et al. reference is not applicable toother carbonaceous and/or feedstock based processes, such asgasification and/or partial oxidation gasifying reactor systems (POX).

One exemplary application of the inventive technology may include thetreatment of carbonaceous materials such as coal to generate acatalytically enhanced low emission carbonaceous fuel. In oneembodiment, the invention provides compositions and methods for reducingemissions of NOx, SOx and Hg among others CCB's that arise from thecombustion of coal. In particular, coal burning facilities such as thoseused by electrical utilities may be used as one exemplary model of thecurrent invention. In a preferred embodiment, for example a typicalpulverized coal-fired facility may be appropriate for the currentinvention. In a typical pulverized coal fired facility, coal may becombusted in an atmospheric air combustion environment, additionally inan oxygen-fired facility, coal is combusted in an enriched oxygenenvironment by using pure oxygen diluted with combustion air or gas orperhaps flue gas (Hot/Cold RFG).

Again, as shown in FIG. 1, flue gas (FG), which may be a combination ofcombustion gases, air and various particulate matter such as fly ash maybe shunted through a convection pathway where heat may be removed fromthe flue gases. It should be noted that, as shown in FIG. 2, such aconvection pathway is generally characterized by a plurality of “heat”zones characterized by the temperature of the gases and combustionproducts in each zone with greater temperatures nearer the combustionevent and falling generally downstream. As noted in FIG. 1, such aconvective pathway may contain a variety of combustion gases, perhapscontaining NOx, SOx and Hg species as well as particulate matter such asfly ash and other constituents moving away from the combustion event. Intypical conventional systems as shown in FIG. 2 below, this flue gas mayundergo various post-combustion treatments, such as chemical scrubbers.Post-combustion sorbant injections may be applied to the flue gas toremove undesired chemical constituents and the like prior toenvironmental release.

For example, again as shown in FIG. 2, typical post-combustion flue-gastreatments may include post-combustion selective catalytic reaction(SRC) treatment, traditional sorbent injection, and post-combustion fluegas desulfurization (FGD). In addition, as shown generally in FIGS. 2-3,further along in the convective pathway, the flue gas and fly ash maypass through lower temperature zones until a baghouse or electrostaticprecipitator is reached before the gases may be emitted to the stack. Inthe US, typical remediation steps generally need to be accomplishedprior to environmental release of the flue gas through the stack.

As an initial matter, coal-fired power plants generate steam produced ina boiler which is further used to generate electricity. In a steamboiler, water is heated under pressure to produce high-temperature andhigh pressure steam, which then passes through a steam turbine thatspins an electric generator. The heat required to produce steam isobtained by burning coal. As noted above, flue gas formed after burningthe coal contains hazardous emissions which are typically treated withpollutant control devices placed after combustion. There are a number oftraditional post-combustion remediation methods.

Mercury speciation may have a strong impact on its capture by airpollution control techniques. Depending on the flue gas conditions Hgmay be present in the flue gas as elemental mercury vapor (Hg⁰), as anoxidized mercury species (Hg²+), and as particulate-bound mercury(Hg^(p)). Elemental Hg, released into the exhaust gas, can then beoxidized to Hg²+ via homogeneous and heterogeneous oxidation reactions.Among these Hg species, Hg⁰ may be difficult to capture due to itsinsolubility in water, high volatility and chemical inertness. Differentcontrol technologies such as filters, desulfuration units and sorbentinjection can be applied to decrease Hg emissions. As one example,mercury is at least partially volatilized upon combustion of coal. As aresult, the mercury tends not to stay with the ash, but rather becomes acomponent of the flue gases. If remediation is not undertaken, themercury tends to escape from the coal burning facility into thesurrounding atmosphere. Depending on the type of coal combusted and Hgspeciation, Hg removal efficiency can show significant variation makingit difficult to find a consistent Hg removal technology for differenttypes of coal burned in different types of boilers or furnaces or otherfuels or fuel uses whether combustion or not.

Two common mercury removal technologies are the addition of scrubbersand carbon injection. However, each of these methods has significanttechnical and economical drawbacks that limit their effectiveness. In atypical carbon injection remediation process activated carbon isinjected into the flue gas stream to adsorb mercury before it exits thestack. While this approach may reduce mercury emissions, it can alsoproduce a significant amount of solid potentially hazardous waste. Forexample, the activated carbon systems may lead to carbon contaminationof the fly ash collected in exhaust air treatments such as the bag houseand electrostatic precipitators. Furthermore, since the fly ash may nowcontain activated carbon, it can no longer be useable in cement and/orconcrete applications, one of the major post combustion utilizationmarkets. Finally, use of such activated carbon systems tends to beassociated with high treatment costs and elevated capital costs. Asnoted above, another typical Hg remedial technique involves thetreatment of the flue gas with wet scrubber or Selective CatalyticReduction (SCR) systems, However, again these approaches are alsocapital intensive—in materials and implementation—and further usehazardous materials such as anhydrous ammonia, and also produceundesired and perhaps hazardous waste products which must be disposedof, often at great expense. Moreover, the present invention may assistutilities in complying with new mercury emission regulations without thehigh capital equipment costs associated with current mercury remediationtechnologies.

Flue gas NOx emissions may be typically controlled by SelectiveCatalytic Reduction (SCR) systems processes. In an exemplary SCRprocess, ammonia (NH₃) reacts with NO and NO₂ gases such as on thecatalyst surface and reduces to nitrogen (N₂) and water vapor (H₂O).Ammonia may be diluted with air or steam and this mixture may beinjected into the flue gas upstream of a metal catalyst bed where itreacts with the flue gas. Oxides of vanadium, titanium, tungsten, orzeolites typically catalyze such as in the following reactions:4NO+4NH₃+O₂→4N₂+6H₂O2NO₂+4NH₃+O₂→3N₂+6H₂ONO+NO₂+2NH₃→2N₂+3H₂OHowever, such methods of NOx reduction are again limited as suchprocesses are typically expensive and require the use of, and alsogenerate hazardous compounds/waste that may require further remediationand/or disposal. Again, the present invention may assist utilities incomplying with new NOx regulations without the high capital equipmentcosts associated with current NOx remediation technologies.

In another remediation example, flue gas SOx removal systems may begenerally separated into dry and wet removal systems depending on theparticular coal's sulfur content. Plants burning low-sulfur coaltypically use dry systems where lime and water are added to the flue gasand the following reactions occur:CaO+H₂O→Ca(OH)₂Ca(OH)₂+SO₂→CaSO₃.½H₂O+1/2H2OTypically the solids formed from the SO₂ reaction may be captured byelectrostatic precipitators or filtration devices such as bag houses. Atypical “wet” SOx removal system may typically be used in plants wherehigh-sulfur coal is burned. Here, water sprayers may be used to saturatethe flue gas, while calcium carbonate (CaCO3) is injected into the fluegas stream. Sulfur dioxide in flue gas may react with the CaCO3 andcalcium sulfite (CaSO3.1/2H2O) may be formed. CaSO3.1/2H2O may beoxidized in a subsequent reaction forming calcium sulfate (CaSO4.2H2O),also known as gypsum, perhaps through the following reactions:CaCO3+SO2+½H2O→CaSO3.1/2H2O+CO2CaSO3½H2O+O2+3/2H2O→CaSO4.2H2OTypical “wet” SOx removal systems however can be limited as theygenerally employ forced oxidation methods to push desulfurization typereactions to maximize gypsum formation. Both dry and wet SOx removalsystems have high capital costs due to the need for expensivenon-corrosive materials in the systems. The present invention may assistutilities in complying with new SOx regulations without the high capitalequipment costs associated with current SOx remediation technologies.

The present invention may assist utilities or other users in reducingthe amount of CO₂ that is produced in a combustion furnace orgasification processes due to the catalytic process which improvescarbon conversion efficiency. For example, particulate matter (PM)emissions consist primarily of fly ash and unburned carbon produced fromburning of coal in a coal fired furnace or boiler and is generally apowdery particulate matter made of the components of coal that do notvolatize upon combustion. The content and amount of ash are a functionof coal properties, furnace-firing configuration and boiler operation.Depending on the boiler type, approximately 50% to 80% of the total ashexits the boiler as fly ash. PM emissions can also be formed from thereactions of SO₂, NO_(x) compounds and unburned carbon particles. PMemissions in coal-fired power plants is normally carried off in the fluegas and is usually collected from the flue gas using conventionalapparatus such as electrostatic precipitators, filtration devices suchas bag houses, and/or mechanical devices such as cyclones. Thisproduction of large amounts of fly ash may be used for secondaryproducts or uses or disposed of. Various attempts to create secondaryproduct streams from this fly ash waste, such as cement production havebeen met with some limited success, however, often the vast bulk of flyash is simply land filled.

As shown above, the generally known systems and techniques for coalcombustion generated NOx, SOx, Hg as well as particulate removal arelimited in several significant ways. First, such systems are generallyexpensive requiring significant capital cost and require not onlyexpensive but sometime dangerous chemicals. As noted above, such systemsalso generally produce hazardous byproducts that must be disposed ofincreasing such systems incremental costs. Furthermore, such systemstypically require additional compliance with government regulationsfurther driving up the cost.

Second, such systems are post-combustion processes requiring additionalexpensive application and removal capabilities. In addition, theeffectiveness of such systems is variable and inconsistent based on thetype of coal utilized at a particular plant limiting the range of coalinputs available for use at a specific plant without significantretro-fitting. Third, as noted, while some synergies do exist, no singlecomprehensive system exists to effectively deal with the variouscombustion byproducts sought to be removed.

In addition, as noted above other processes, such as gasification mayalso consume carbonaceous and/or other feedstocks. Such exemplaryprocesses can occur in the presence of air, which contains nitrogen. Assuch, gasification reactors can create by-products that need to betreated or disposed of due to environmental concerns. For example,during the combustion process, carbon dioxide and nitrogen- and/orsulfur-containing compounds, such as oxides of nitrogen and amines, canbe formed. Environmental regulations more frequently require thecollection and sequestration of carbon dioxide. Amine separator unitswhich are necessary to remove acidic compounds, such as, for example,H₂S and CO₂, are very energy intensive, are large and thus have amassive footprint, and can be very costly to operate and maintain. Asnoted above, the following invention may not only, in some embodimentsreduce harmful emissions resulting from the process, but may alsoimprove CO formation, perhaps through a catalytic and/or sorbing processor other process as will be explored below.

Additional embodiments of the inventive technology may include thetreatment of carbonaceous and/or other feedstocks for use ingasification, pyrolysis and/or reformation processes. For example,“gasification” herein generally relates to a variety of gasifier systemssuch as GE gasifier and/or Texaco gasifier referenced generally in theattached IDS and herein incorporated in their entirety by reference.Such systems may generally utilize carbonaceous materials such as forexample coal or coke to form select product gas components such ascarbon monoxide, hydrogen gas or synthesis gas (syngas), which can beused to produce electricity in an integrated gasification combined cycle(IGCC) process or as a starting point in many chemical processes.

Gasification emphasis again came to the forefront due to the energycrisis of the 1970's. Gasifier technology was perceived as a relativelycheap alternative for small-scale industrial and utility powergeneration, especially when sufficient sustainable biomass resourceswere available. By the beginning of the 1980's nearly a dozen (mainlyEuropean) manufacturers were offering small-scale wood and charcoalfired “steam generation” power plants. In Western countries, coalgasification systems began to experience expanded interest during the1980's as an alternative for the utilization of natural gas and oil asthe base energy resource. Technology development perhaps mainly evolvedas fluidized bed gasification systems for coal, but also for thegasification of biomass. Over the last 15 years, there has been muchdevelopment of gasification systems directed toward the production ofelectricity and generation of heat in advanced gas turbine basedco-generation units.

As shown in FIG. 1, generally the gasification process may involve thecontrolled heating of carbonaceous fuels and/or feedstock in the absenceof oxygen or reduced oxygen, resulting in thermal decomposition of thefuel into volatile gases and solid carbon material by-product. As notedabove, a typical gasifier may convert carbonaceous fuels and/orfeedstock into gaseous components by applying heat under pressure in thepresence of steam.

A traditional gasifier differs from a combustor in that the amount ofair or oxygen available inside the gasifier may be controlled so thatonly a relatively small portion of the fuel burns completely. This“partial oxidation” process provides heat to further the process. Ratherthan burning, most of the carbon-containing feedstock is chemicallybroken apart by the gasifier's heat and pressure, setting into motionchemical reactions that produce primarily hydrogen and carbon monoxide,and other gaseous constituents. Such gasifier systems may involvecombustion while others do not involve a combustion pathway.Gasification reactors can convert generally solid feedstocks intogaseous products. For example, gasification reactors can gasifycarbonaceous feedstocks, such as coal and/or petroleum coke, to producedesirable gaseous products such as hydrogen and carbon monoxide and someamounts of methane. Gasification reactors generally need to beconstructed to withstand the significant pressures and temperaturesrequired to gasify solid feedstocks. Generally, carbon in the coal orcoke can be converted into gas by partial combustion with oxygen.

In an exemplary gasification process, carbonaceous or other feedstocksundergo a combustion process as the volatile products and some of thechar may react with oxygen to form carbon dioxide and perhaps a smallamounts of carbon monoxide, which may further provide heat for thesubsequent gasification reactions.C+O₂→CO₂ andC+½O₂→CO

In this process carbon also can react with water in an endothermic watergas reaction to perhaps produce carbon monoxide and hydrogen, via thereaction.C+H₂O→H₂+CO

A shift reaction may then convert all or part of the carbon monoxideinto hydrogen to reach equilibrium.CO+H₂O→CO₂+H₂

The results of this final mixture may comprise hydrogen and carbonmonoxide and may be referred to generally to as synthesis gas or syngas.Additional general reference to various gasification examples may befound in U.S. Pat. No. 7,638,070 and the accompanying provisional IDSincorporated herein in their entireties by reference.

As will be discussed in more detail below, the present inventionovercomes the limitations of the prior art and provides a novel andpreviously unrecognized improved treatment of carbonaceous fuel and/orfeedstock sources that may result in the reduction and/or prevention ofNOx, SOx and Hg emissions among other CCB's.

SUMMARY OF INVENTION

In some embodiments, the present invention may provide for theprocessing of carbonaceous and/or feedstock fuel sources with catalyticadditives of segregated particulate matter source compounds such assegregated fly ash combined with calcium source compound, such assegregated limestone such that they are distributed across the surfacearea of said processed carbonaceous fuel particulate forming acatalytically enhanced low emission carbonaceous fuel. Such treatmentmay occur perhaps pre-consumption—which may include both combustion andnon-combustion gasifier processes—and may chemically modify theconsumption event resulting in catalytically or otherwise enhancingreactions that lead to the reduction in the formation of NOx, SOx and Hgemissions compared to combustion of a non-treated carbonaceous fuel.

In other embodiments, such treatment may provide improved catalyticactivity energetically favoring reactions resulting in the reduction of,for example NOx and/or mercury emission formation and the like. Suchimproved catalytic or other chemical reactivity properties may be theresult of increased surface area contact of the segregated constituentchemicals during combustion of pre-treated coal. Improved catalytic orother chemical reactivity properties may also be a result of thechemical composition of, as well as self- and cross reactivity of saidsegregated constituent and carbonaceous fuel during processing and/orduring combustion and/or gasifying. Such catalytic enhancements may alsoresult in the reduction of various sulfur compounds such as sulfuroxides (SOx) (including, but not limited to SO, SO₂, SO₃, S₇O₂, S₆O₂,S₂O₂, and the like). In additional embodiments, such carbonaceous fueltreatment may result in the enhanced removal of Hg species, perhapsacross a baghouse. The incorporated fly ash may or may not be indigenousto a specific coal-fired production facility creating value-added use ofnormal coal combustion waste streams as well as providing significantcost savings in raw materials. Moreover, as discussed below, suchtreatment steps may be performed in situ at a point of productionlocation, such as a mine. Finally, still further embodiments mayfacilitate the formation of syngas and improved production of selectproduct gas components, which may also contain reduced amounts of, forexample NOx, SOx, and mercury containing emissions.

Some embodiments may further be coupled with other known or traditionalremediation processes, techniques and/or compounds to synergisticallyreduce, for example NOx, SOx, and/or Hg production and/or CCB's fromtypical carbonaceous and/or feedstock fuel sources consumption processesand especially those of pulverized coal furnaces. All of the forgoingembodiments may be automated as well as configured to be adaptable topre-existing pulverized or other coal-fired production facilities,gasifier, POX reactors and the like as well as different species ofcarbonaceous and/or feedstock species as well as non-combustionprocesses such as gasification. Additional areas of applicability willbecome apparent as discussed below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: is a diagram of a generic gasification process in one embodimentthereof;

FIG. 2: is a simplified oxygen-fired combustion system in one embodimentthereof;

FIG. 3: is a diagram of traditional post-combustion flue gas treatmentsin one embodiment thereof;

FIG. 4: is a diagram of an exemplary pulverized coal-fired systemincluding particulate matter removal systems in one embodiment thereof;

FIG. 5: is a list of an exemplary pre-combustion carbonaceous fueltreatment chemical profiles in one embodiment thereof;

FIG. 6: is a list of exemplary carbonaceous fuel treatment mix profiles;and

FIG. 7: is a list of exemplary fly ash composition ranges; and

FIG. 8: is an exemplary model of devolatilization.

DETAILED DESCRIPTION OF THE INVENTION

The present invention includes a variety of aspects, which may becombined in different ways. The following descriptions are provided tolist elements and describe some of the embodiments of the presentinvention. These elements are listed with initial embodiments, howeverit should be understood that they may be combined in any manner and inany number to create additional embodiments. The variously describedexamples and preferred embodiments should not be construed to limit thepresent invention to only the explicitly described systems, techniques,and applications. Further, this description should be understood tosupport and encompass descriptions and claims of all the variousembodiments, systems, techniques, methods, devices, and applicationswith any number of the disclosed elements, with each element alone, andalso with any and all various permutations and combinations of allelements in this or any subsequent application.

One embodiment of the invention may include a method of generating acatalytically enhanced low emission carbonaceous fuel. In one embodimentthereof, this may be accomplished by processing a carbonaceous fuel inthe presence of a segregated particulate matter source compound and asegregated calcium source compound, which may be any calcium containingcompound or calcium impregnated particles or product, such that they aredistributed across the surface area of said processed carbonaceous fuelparticulate forming a catalytically enhanced low emission carbonaceousfuel. Combusting said catalytically enhanced low emission carbonaceousfuel wherein said step of combustion results in the reduction of NOxemissions compared to combustion of a non-treated carbonaceous fuel aswell as the reduction mercury emissions compared to combustion of anon-treated carbonaceous fuel among others. In some embodiments, thereduction of NOx and/or mercury emissions may be accomplished, forexample through catalytic action, perhaps resulting in: catalyticallyreducing nitrogen oxidation compared to consumption (combustion, partialcombustion and/or non-combustion gasification and/or partial combustiongasification) of a non-treated carbonaceous fuel; catalytically reducingNOx formation; catalytically increasing nitrogen reduction;catalytically increasing the decomposition rate of NOx; catalyticallyincreasing the decomposition efficiency of NOx; catalytically reducingmercury species formation; catalytically reducing mercury oxidationreactions; catalytically reducing mercury reduction reactions;catalytically reducing mercury volatilization; increasing the efficiencyof traditional remediation and/or capture processes and systems for NOx,SOx, mercury and other CCB's outline above.

By way of example, majority of NOx emissions from coal-fired powerplants may be derived from the nitrogen present in the coal (known asFuel and Prompt NOx), not from the nitrogen introduced with the air(Thermal NOx), which is opposite the case for internal combustionengines, where essentially all of the NOx is thermally formed fromnitrogen in the combustion air. Both Fuel NOx and Prompt NOx may formfrom nitrogen derived from the coal and are released during thedevolatilization step of coal combustion. The nitrogen is released fromthe coal in many different volatile forms, including light gases (NH₃,N₂O, NO, etc.), light aromatics such as pyrolle and pyrazene, andimbedded in tars as pyrrolic and pyridinic bound nitrogen. These tarsmay be quickly consumed by the oxygen in the flame, which yields hightemperatures at the base of the flame and attaches the flame securely tothe burner. Fuel NOx may be formed when oxygen reacts with the nitrogenin the volatiles to convert it to forms that lead along a pathway that,for example may create NO. Prompt NOx may be formed when nitrogen involatiles on the edge of the flame front encounter a high oxygenconcentration and are oxidized at that location to form NO or otherproducts that may rapidly transform to NO.

The stop of, in this example coal devolatilization may generally takeplace in the first 25 ms of combustion, as the pulverized coal particlesare entering the burner. The rapid heating rate may be important forsignificant volatile yield, which is often much greater than thatobtained from a proximate analysis. As the devolatilization event ends,the remaining material from each coal particle may solidify andcrosslink to form a solid porous char particle that may takeapproximately 2 seconds to burn out, and the NO formed from oxidation ofthe char may be difficult to control.

As noted previously, a common approach to reducing NOx emissions is tocreate a reducing zone in the base of the flame where the volatiles arereleased, which may drive the nitrogen in the volatiles along a pathwaythat leads to the formation of N₂ rather than NO. This approach may mosteffective when combined with conditions that lead to a high volatilesrelease from the coal, such as higher temperatures at the base of theflame. One way to enhance this approach is to add volatiles to the fuelin the form of fuels that are primarily volatiles, such as oils orbiomass solids. The additional volatiles may tend to make the base ofthe flame more reducing, yet create an even hotter base flame andincrease the volatile yield of the coal, releasing more of the coalnitrogen in that section of the furnace and more efficiently convertingit to N₂.

Another way to enhance the staging approach to reduce NOx, as describedgenerally herein is to add a catalyst to the coal that will enhance coaldevolatilization, by breaking the carbon bonds forming the coal, whichwill cause the coal to breakdown into metaplast (volatile and tarprecursor) quicker and to a greater extent than it would without thecatalyst. As noted elsewhere, iron oxide may an effective catalyst forthis purpose. Moreover, calcium oxide may also be effective as acombustion or devolatilization catalyst and further calcium and iron mayeffectively catalyze the transformation of the organically boundnitrogen in coal into diatomic nitrogen gas.

In certain embodiments these catalysts are able to directly catalyze theconversion of char-bound nitrogen to nitrogen gas, while in otherembodiments the catalytic reduction may be accomplished throughincreasing the volatile yield significantly reducing the NOx formationif the burner or furnace was, for example staged for low-NOx emissions.The catalytic enhancement of devolatilization increases the percentageof nitrogen released with the volatiles and makes the base of the flamemore reducing by increasing the volatiles, both of which tend to driveNOx lower in a staged flame or furnace.

As noted, in some embodiments fly ash contains iron oxide, calciumoxide, and titanium oxide, all of which are combustion, gasification,and pyrolysis enhancing catalysts. In certain embodiments, theircatalytic effect is achieved through alteration of their physicalproperties, specifically, one embodiment (1) the fineness of thesegregated material added and its dispersion and/or adhesion to thesurface of the pulverized coal particles, (2) the availability ofcatalyst material on the surface of the additive, for example flyash maybe included inside a silica and alumina shell, (3) the activity of thecatalytic material, and (4) the active catalytic surface area.

In some embodiment, if an inert powder or segregated particulate matterand/or calcium source compound may be applied to the coal. Suchconstituents may take physical residence of locations on coal particlesand occupy a significant fraction of the external coal-particle surface,thus preventing the active catalyst from locating at those active sitesand reducing its effectiveness as a catalyst additive.

In one embodiment, the inventive technology may affect thedevolatilization of a carbonaceous fuel. In one exemplary model, NOx maybe generated from the combustion of coal. In general NOx may begenerated through three different ways: thermal NOx, prompt NOx andfuel-NOx. Thermal NOx refers to NOx formed with reactions between N2 andO2. Its formation may be dominated by the combustion temperature whichis effective above 1400° C. Prompt NOx refers to the reaction between N2and hydrocarbon radicals such as CHi. Prompt-NOx usually accounts for avery small part of overall NOx emissions from coal combustion undertypical operating conditions. Fuel-NOx comes from nitrogen species boundin fuel. In pulverized coal devolatilization, fuel-N may divided intovolatile-N and char-N. As generally shown in FIG. 7, during combustionprocess, the volatile-N transforms into either NO and N₂, while char-Ngoes through the heterogeneous reactions along with the char oxidation.In conventional coal combustion, fuel-N is the dominant source for NOproduction with the thermal-N as a minor contributor. In oxy-coalcombustion, N2 is substitute by the recycled flue gas which the maincomponent is CO2 and H2O. So the NO may be formed by fuel-N in theory.Air entrainment in the burners and milling system may give rise toincreased NOx emission due to thermal-N formation.

In one embodiment, the alteration of the devolatilizationprocesses/profile of a carbonaceous fuel may be catalytic in nature, forexample by energetically favoring certain reactions that result in thereduction in NOx or other emissions. In other embodiments, alteration ofthe devolatilization process may include the physical interruption ofcertain chemical constitutes, perhaps due to the close proximity andassociation of segregates particulate and calcium source matterassociated with the carbonaceous fuel. In another embodiment, theinventive technology may prevent the devolatilization of fuel bound(fuel-N) nitrogen into Char-N and/or Vol-N. In still further embodiment,the inventive technology may prevent the conversion of Char-N and/orVol-N into NOx compounds.

Another embodiment of the invention may include a method of generating alow emission carbonaceous fuel additive. Generation of such a lowemission carbonaceous fuel additive may include the steps of segregatinga quantity of particulate matter source compound and a quantity ofsegregating calcium source compound (or perhaps segregating non-halogencontaining calcium source compound) and distributing the segregatedparticulate matter source compound and the segregated containing calciumsource compound across the surface area of a carbonaceous fuelparticulate forming a catalytically enhanced low emission carbonaceousfuel. Combusting said catalytically enhanced low emission carbonaceousfuel wherein said step of combustion results in the reduction of NOxemissions compared to combustion of a non-treated carbonaceous fuel aswell as the reduction mercury emissions compared to combustion of anon-treated carbonaceous fuel among others.

Another embodiment of the invention may include a method of in situtreatment of carbonaceous fuel at a point of production. This may beaccomplished through one or more of the following steps includingestablishing a quantity of particulate matter source compound from thecombustion of a carbonaceous fuel then segregating said quantity ofparticulate matter source compound as well as establishing andsegregating a quantity of calcium source compound. Treatment of acarbonaceous fuel may occur in situ, or at the location of a point ofproduction such as a mine or storage, transport, or processing facility.In some applications. This in situ treatment may include combiningsegregated particulate matter source compound and/or said segregatedcalcium source compound with of said carbonaceous fuel as well asperhaps adhering the segregated particulate matter source compoundand/or segregated containing calcium source compound to a carbonaceousfuel, perhaps through through application of a binding agent. Though, asdiscussed below, such adhering step may be mitted in certainembodiments, for example where the transport distance is short so as tomitigate loss of treatment constituents en route, as well as perhapswhere a treated carbonaceous fuel has been allowed to dry therebyperhaps adhering onto the surface of the fuel. Again, in certainembodiments the treated carbonaceous fuel may be transported to acombustion facility to be processed. Examples of such processing mayinclude one or more of the following: mixing; crushing; grinding;milling; grinding; and/or compressing. In a preferred embodiment saidstep of processing may include pulverization which may further includeone or more of the following pulverization processes: low speedpulverization; medium speed pulverization; high speed pulverization;ball pulverization; tube pulverization; ring and ball pulverization;vertical spindle roller pulverization; bowl pulverization; attritionpulverization; impact pulverization; and/or hammer pulverization.

Such step of processing a treated carbonaceous fuel may allow the boundsegregated particulate matter source compound and/or the segregatedcontaining calcium source compound to be distributed and/or dispersedacross the entire surface area of the carbonaceous fuel particulateforming a catalytically enhanced low emission carbonaceous fuel. Asnoted above, combusting said catalytically enhanced low emissioncarbonaceous fuel wherein said step of combustion results in thereduction of NOx emissions compared to combustion of a non-treatedcarbonaceous fuel as well as the reduction mercury emissions compared tocombustion of a non-treated carbonaceous fuel among others.

In various embodiments, the invention provides systems, compositions,and methods for reducing emissions of NOx, SOx and Hg and perhaps otherCCB's that arise from the combustion of coal or through gasification. Inparticular—as noted above—coal burning facilities such as those used byelectrical utilities may be used as exemplary model of the currentinvention. Further, embodiments adapted to pulverized coal furnaces maybe particularly significant. In addition, it should be noted that suchexamples are not limiting, as the current invention may be applied to avariety of commercial and industrial processes that may utilizecombustion of coal, or other carbonaceous compounds resulting inproduction or NOx, SOx or Hg emissions individually or collectively.Another example would be the Texaco/General Electric pulverized coalslurry partial oxidation gasification reactor or generally a partialoxidation reactor (POX). In a preferred embodiment, the currentinventive technology may provide for the pre-combustion treatment ofcoal resulting in greater than, or at least a 40% reduction in Hg, andgreater than, or at least 20% reduction in NOx, as well as a measurablereduction in SOx emissions that result from the modified combustion ofcoal as compared to untreated coal. It should be noted that thefollowing percent reductions in the above mentioned chemicalconstituents is merely exemplary and are in no way limiting.

As noted above, in a typical coal-fired facility, and especially apulverized coal furnace facility, coal combustion results in theproduction of particulate matter such as fly ash which typically isconsidered a secondary waste stream and must be re-purposed or disposedof through land filling or other appropriate methods. It should be notedthat the terms particulate matter may encompass numerous combustionand/or gasification by-products as well as other particles than NOxand/or mercury and/or SOx and/or other CCB emissions.) In one embodimentof the current invention, fly ash from coal combustion may be collectedand re-purposed for the pre-combustion treatment of coal. As referencedgenerally in FIG. 6, the exact compounds present in any given fly ashsample may vary across various facilities and may further be influencedby variables such as temperature, coal used, combustion temperature,collection techniques employed and the like, a fly ash sample resultingfrom typical coal combustion may contain the following general chemicalprofile: Silicon Dioxide (SiO2); Aluminum Oxide (Al2O3); Iron Oxide(Fe2O3); Calcium Oxide (CaO); Magnesium Oxide(MgO); Potassium Oxide(K2O); Sodium Oxide (Na2O); Titanium Dioxide (TiO2); Sulfur Trioxide(SO3); Phosphorus Pentoxide (P2O5); Strontium Oxide (SrO); Barium Oxide(BaO); Manganese Oxide (MnO); and/or Other Trace Chemicals.

It should be noted that many different types of fly ash may becontemplated such as fly ash from other carbonaceous combustion as wellas non-combustion process as well as perhaps fly ash from biomass, woodand/or other feed stocks. In one preferred embodiment, the collected flyash may be introduced to pre-combustion coal and further act as acatalytic agent reducing the formation of NOx species during combustionamong others. For example, the iron and calcium oxides may be presentand act as a catalyst to reduce NOx formation and/or emissions.Principally, presence of Iron compounds in various forms may control NOxemissions through decreasing the conversion rates of char-N, tar-N, HCN,and NH3 to NOx. In addition, calcium oxide (CaO) and/or (Fe2O3) may actto reduce NOx formation perhaps through the catalytic decomposition ofperhaps nitrous oxide (N₂O). It should be noted that each of theindividual chemical constituents may act independently and/orsynergistically in combination to produce the above referencedemission/formation reductions. For example, in one embodiment mayinclude the step of processing segregated particulate matter sourcecompound and a segregated calcium source compound such that they aredistributed across the surface area of a processed carbonaceous fuelparticulate forming a synergistic interaction between a quantity ofsegregated fly ash and a quantity of segregated limestone and acarbonaceous fuel resulting in the reduction of NOx, and/or mercuryemissions compared to consumption of a non-treated carbonaceousmaterial.

In another embodiment, such fly-ash may combine with a carbonaceous fuelsource, such as coal—perhaps having been previously pulverized and/ormilled together—such that the association of said segregated fly ashwith such coal particles may act as a catalyst or initiate otherprocesses to energetically favor formation of elemental nitrogen as N₂as opposed to NO or another NOx compound. In additional embodiments suchreaction may be accomplished through the synergistic action and/orinteraction of any of the fly ash constitutes and, for example,carbonaceous particles or fuel source.

In additional embodiments, a segregated particulate matter sourcecompound and a segregated calcium source compound treatment may act toform a catalytic film and/or a synergistic catalytic film and/or acatalytically active adsorbate film across the surface area of saidprocessed carbonaceous fuel particulate. Certain embodiments thiscarbonaceous fuel particulate may include carbonaceous gas particulate,carbonaceous liquid particulate, and/or carbonaceous solid particulate.In a preferred embodiment, a carbonaceous fuel particulate may includeone or more of the following: coal particulate, pulverized coalparticulate, milled coal particulate, crushed coal particulate, groundcoal particulate, and/or compressed coal particulate. In someembodiments, such catalytic films may alter, such as increasing and ordecreasing the chemical and/or even atomic interactions of combustioncontaminants and/or other consumption produced compounds compared toconsumption of a non-treated carbonaceous materials.

In one embodiment, segregated particulate matter source compound such asfly ash may adsorb various atoms, ions, or molecules from a gas, liquid,or dissolved solid such as to its surface. The resultant adsorbate onthe surface of the adsorbent fly ash may act to sequester, for exampleNOx, SOx or Hg species, or perhaps position such species in an adsorbatefilm in such a manner as to allow energetically favorable reactions withother chemical constituents resulting perhaps in the reduction in theaforementioned compounds. Additional chemical, adsorption and/or othercatalytic reactions resulting in the reduction of NOx, SOx, Hg and otherCCB's, while not explicitly stated are contemplated within the scope ofthis disclosure.

In one embodiment of the current invention it may be advantageous toincrease the available surface area of the selected fly ash prior topre-combustion treatment of the coal. Such surface area increase may beaccomplished through the pre-combustion treatment of coal with finelypulverized, and/or milled segregated particulate matter. Such segregatedparticulate matter source compound generally being referred to assegregated particulate matter source compound. In one example, collectedfly ash may be segregated by separating the fly ash into variously sizedparticles. Such particle size may be accomplished through meshsegregation, grinding, blasting, gradient or centrifugal separation,cyclone separation, and other known pulverization, milling and/orsegregation techniques. As noted, in one preferred embodiment, thissegregation may be accomplished through passing the raw fly ash througha mesh system. For example, in a mesh system, the mesh number representsthe number of openings or the like of a mesh across a linear inch ofscreen. For example, a typical mesh to micron conversion may have avalue of “100 mesh” which may exhibit approximately 100 openings in alinear inch of mesh screen. Taking into account for varying wirethickness, an approximate size of particle can be isolated using saidscreen mesh. Returning to the following example, particles passingthrough a 100 mesh may isolate a group of particles of approximately˜149 microns and smaller. While a variety of mesh and size ranges arecontemplated within the invention, however, in a preferred embodiment anapproximate maximum and/or minimum segregated particulate matter sourcecompound size range of 100 μM to 0.5 uM as generated by theircorresponding mesh value is contemplated within this disclosure. Rangesfor such sizing also exist with the disclosure and as part of theinvention are explained below.

Increasing the available surface area may enhance the catalyticproperties of the segregated particulate matter source compound duringsubsequent coal combustion. Such enhanced catalytic and/or sorptionproperties may be a result of the enhanced distribution of theaforementioned segregated particulate matter source compound treatmenton said carbonaceous fuel and/or feedstock such as coal, while inadditional embodiments, such segregated particulate matter sourcecompound may be milled and/or pulverized with said carbonaceous fuelprior to combustion resulting in perhaps, in the enhanced distributionof the segregate particles across the surface of the pulverized coalparticles, or even more uniform distribution within the combustionfurnace and/or resulting convection pathway. In addition, treatment ofsuch carbonaceous fuel and/or feedstock may promote combustion,gasification, or pyrolysis or other high efficiency contact and/orchemical positioning with combustion by products. This enhanced surfacearea and distribution may result in the overall reduction of NOx, SOxand Hg species and other CCB's constituents of the flue gases asdiscussed previously.

Another embodiment of the inventive technology may include thepre-combustion treatment of carbonaceous fuel and/or feedstock withsegregated calcium source compound, such as limestone to facilitate thenon-formation/removal of NOx, SOx, Hg species and the like. In apreferred embodiment such segregated calcium source compound may act asa source of non-halogenated calcium (Ca) as well as other sourcematerials that may generally interact with, inhibit the formation of,and/or facilitate the removal of NOx, SOx, and Hg species among othersCCB's. While various types of limestone may be contemplated, any suchappropriate source of the general segregated calcium source compoundconstituents, such as those found in limestone may be used individuallyor collectively. For example, in a preferred embodiment segregatedlimestone may act as a source of: Calcium Carbonate (CaCO3); Magnesiumcarbonate (MgCO3); Crystalline Silica (Si); other trace compounds.

In certain embodiments the segregated calcium source compound may bepulverized, milled or otherwise segregated, perhaps utilizing the sameor similar mesh or cyclone system described above. In this embodiment,the aforementioned segregated calcium source compound particles may bevariable in size, perhaps ranging from 100 μM to 0.5 uM or any desiredmesh value. Such particle size may be accomplished through meshsegregation, grinding, blasting, gradient or centrifugal separation,cyclone separation, and other known pulverization, milling and/orsegregation techniques. It should, however, be noted that based on thecharacteristics of mesh segregation pulverization, and/or milling, anyresultant segregated material, whether it be, for example fly ash orlimestone may represent a range of particle sizes with the meshgenerally only providing an upper size limit. In some instances thelower limit of the particle size may include perhaps even individualatomic units.

Similar to the discussion of segregated particulate matter particlesabove, such discussion is merely exemplary and not in any way limitingon the wide scope of contemplated type, sizes or combinations ofparticle sizes encompassed in this disclosure. In this regard, suchfinely segregated calcium source compound particles may enhance theremoval of Hg perhaps by helping to retain mercury in the carboncollected as the flue gas passes through a bag-house. In additionalembodiments, calcium source compound source provided in the limestonemay provide for a catalytic or other pathway to prevent the formation ofmercury species in the first place. In still further embodiments, suchmercury species may be captured by a calcium source, sorbed on thecalcium, and/or perhaps processed in the absence of a halogen such asbromine. In still further embodiments, the segregated calcium sourcecompound treatment of the coal pre-combustion may act as ancatalytically active adsorbate film, perhaps in conjunction with saidsegregated particulate matter providing catalytic sites to facilitatingbinding and remediation reactions of certain mercury species, as well ascapture, for example through a baghouse system. In one embodiment,adding limestone to a carbonaceous fuel, such as pulverized coal, mayduring combustion convert to calcium oxide in the furnace andsubsequently may increase the calcium oxide concentration in thebaghouse filter cake. In certain embodiments, this calcium may enhancethe ability of the unburned carbon (UBC) in the fly ash to retainmercury adsorbed on its surface. Such increased reduction of mercuryemissions may be at least ore greater than 40% in some embodiments,though a variety of ranges may be achieved.

In another preferred embodiment, the segregated calcium source compound,such as segregated limestone may work synergistically with thesegregated particulate matter source, compound such as fly ash toprevent the formation of, or enhance the removal of NOx, SOx, Hg andCCB's formed during carbonaceous fuel combustion and/or gasification.For example, while a variety of amounts and ratios may be contemplated,in an exemplary embodiment approximately 10 lbs of segregatedparticulate matter source compound and said segregated calcium sourcecompound (collectively additive) may be added per ton of carbonaceousmaterial. In addition, as one example, for example 7.5 lbs. or 75% ofsuch pre-combustion coal treatment substance may be comprised ofsegregated and perhaps indigenous fly ash, while the remainingapproximately 2.5 lbs or 25% may be comprised of segregated limestone.Further, by way of non-limiting example, as shown in FIG. 4, varyingpercent ratios of individual fly ash and limestone may be contemplated,for example, in a preferred embodiment the individual constituents'reference in FIG. 4 may form the aforementioned treatment. Ranges forsuch compositions also exist within this disclosure and as part of thisinvention again as demonstrated generally in FIG. 4. Such examples aremerely exemplary in nature and are in no way limiting on the variety ofcombinations contemplated within this application.

In certain embodiments the pre-combustion catalytic treatment of coalmay even result in a reduction of furnace temperatures, for example in acoal boiler. In some embodiments, furnace temperature may remain largelyconsistent with untreated coal at positions close to the base of theflame and at the furnace exit. Such selective temperature alterationsmay also serve to prevent the formation of, and/or facilitate removal ofvarious undesired NOx, SOx, and Hg species among other CCB's. In otherembodiments, increases in carbon-monoxide (CO) formation may occur afterpre-combustion treatment within the flue gas. In some instances, suchadditional formation of CO may prevent the formation of, and/orfacilitate removal various undesired NOx, SOx, and Hg species amongother CCB's. In additional gasification applications, suchpre-consumption treatment may allow the gasification process to proceedunder lower temperatures reducing, perhaps undesired byproducts as wellas conserving energy and capital expenditures.

As noted above, in a preferred embodiment, treatment of the carbonaceousfuel and/or feedstock with segregated particulate matter sourcecompound, segregated calcium source compound or a combination of the twomay occur pre-combustion. However, such embodiment is merely exemplaryas such treatment may also occur concurrently with the carbonaceous fuelor feedstock combustion, post combustion, or at any point along asubsequent convection pathway or even after the bag house and/orelectrostatic precipitators which may be typical of coal combustion. Itshould further be noted that the pre-combustion treatment of coal mayoccur through a variety of combinations, mixtures, methods andtechniques. For example, in one preferred embodiment, a mixture ofsegregated fly ash and segregated limestone may be introduced to coal asit is being fed into, for example a power plant. In some instances, suchtreatment may occur prior to, or simultaneously with the carbonaceousmaterial, such as coal entering a pulverizer before to being directed toa furnace. In some embodiments, treatment may include both dry and wetapplications. For example, in one embodiment, segregated fly ash may becombining with coal in a dry “powered” form, followed by the combiningof segregated limestone through, perhaps a slurry of water or othermaterial. In this preferred embodiment such limestone impregnated slurrymay also act as a dust suppressor for the ultra-fine segregated fly ash.In a preferred embodiment a segregated fly ash, and/or segregatedlimestone may be solubilized. Moreover, such uses of, for examplesegregated fly ash may prevent costly landfilling and/or pond storage.Other embodiments may include wetting a quantity of segregatedparticulate matter source compound and a segregated calcium sourcecompound. Additional embodiments may include the step of adhering asegregated particulate matter source compound and/or segregatedcontaining calcium source compound to a carbonaceous fuel, for exampleprior to combustion and/or even processing through application of abinding agent. Such step may be accomplish in situ at a point ofproduction, such as a mine or prior to transport to a consumptionfacility. Examples of such binding agents may include or more of thefollowing: glue; adhesive; asphalt, coal tar; coal pitch, pitch, starch,magnesia, lignin, montmorillonite, attapulgite, bitumen, and/or wax.

As noted above, in a preferred embodiment indigenous fly ash from acoal-fired facility may be harvested and segregated on-site prior totreatment. Limestone may be established for example through a supplier,for example in a powdered form at a desired particles size and/or may besegregated on-site prior to treatment. Naturally, as can be appreciated,all segregated particles sizes may be altered in various ratios toprovide an optimized result based on the NOx, SOx, Hg or other harmfulemission profile of a particular facility. Such alterations may beautomated as well. In addition, the length, amount, and duration ofpre-combustion treatment may be altered so as to optimize removal ofNOx, SOx, Hg and the like. Additional considerations, such a furnace andcoal type as well as coal content may be used to alter the varyingtreatment parameters. In certain embodiments, real- and/or approximatelyreal-time monitoring of a coal-fired facility may be employed toautomatically alter any treatment parameter. Additional embodiments mayinclude the further impregnation of the fly ash and or limestoneadditives with additional additives to reduce the formation and orincrease removal or perhaps prevention of compounds such a NOx, SOx, Hgspecies and the like. Such impregnated segregated particulate mattersource compound may include known chemical catalytic compounds and/orsorbant/sorbent materials or any compound that may result in a desiredcombustion modification. In another certain embodiments thepre-combustion treatment materials may be captured and re-used, forexample, for additional pre-combustion treatment of carbonaceous fueland/or feedstocks, and or disposed of through traditional processesknown within the industry.

Additional embodiments may include not only indigenous sources ofsegregated particulate matter source compound, but various types andkinds of segregated particulate matter source compound perhaps derivedeven various blends of disparate classes of segregated particulatematter source compound. In one preferred embodiment, fly ash derivedfrom the combustion of bitumous, subbituminous and/or lignite coal maybe blended with fly ash from disparate sources. Such fly ash hybridblends may be monitored and adjusted to achieve a desire level ofeffect, such as the non-formation and or reduction of of NOx, SOx and ormercury emissions.

In one preferred embodiment, treatment constituents, such as segregatedparticulate matter source compound and said segregated calcium sourcecompound may be milled with, for example a carbonaceous fuel and/orfeedstock prior to combustion so as to distribute the constituentsacross the surface area of processed carbonaceous fuel particulates. Inone such preferred embodiment, segregated fly ash and segregatedlimestone may be pulverized, and/or milled in conjunction with coalprior to injection into a furnace for example. In other embodiments,such fly ash and limestone may be segregated then applied to acarbonaceous and/or feedstock fuel source—in this embodiment coal—priorto milling and/or pulverization. In this embodiment, such forcedinteraction may form enhanced interface and/or bonding with thepulverized coal particles such that they are in close proximity perhapsphysically touching one another. In some embodiments, such closeproximity contact may be the result of electro- and/or magnetic- and orchemical attractions. In addition, in some preferred embodiments the flyash may be wetted to facilitate such binding characteristics. In thismanner, in a preferred embodiment segregated fly ash and/or segregatedlimestone and/or a combination of both may form a hybrid formationfacilitating the catalytic and/or adsorption or other chemicalattributes described herein. In a preferred embodiment, sufficientpre-consumption treatment constituents may be added and milled, withperhaps coal, to maximally cover the coal particles surface. A specificrange of segregated fly ash and limestone particle size may be achievedto optimize the desired catalytic and/or adsorption or other propertiesof the treatment. In certain embodiments, such a standard size for thetreatment additives and/or coal particle may be 70% passing through a200 mesh screen. It should of course be noted that such optimization mayvary from combustion, to non-combustion processes, as well as systemsthat employ, for example, liquid fuels such as natural gas and the like.

In additional embodiments, for example, additional additives and/orsegregated additives may be considered such as alumina, as well as lime,lime kiln dust, cement, pumice, and a combination of cement and pumiceor other rare earth metals. For example, iron as well as, perhaps otherrare earth elements/metals such as platinum, silver may act as acatalyst to convert NOx to N2+O2. In some embodiments such catalysts mayutilize compounds such as alumina which may have high oxygen storage topromote the reaction. For example, iron oxide may be present in certainkiln dusts as well as pumice that may also be acting as a promoter. (Forexample, alumina may be approximately 4% of kiln dust. In turn, kilndust may also have approximately 2% iron oxide and perhaps 40% to 50%lime. Pumice may have approximately 12% alumina, 2% iron oxide, andvirtually no lime). In other embodiment, such rare earth metals may bepresent in the coal fly ash. For example, conversion of NO to N₂ mayoccur after combustion such that any alumina and/or iron oxide presentmay coat the boiler and flue along with perhaps rare earth elements.

In one preferred embodiment, the pre-combustion addition of segregatedfly ash from a San Juan Power Plant and a certain amount of segregatedlimestone distributed across the surface area of processed coal mayachieve at least a 20% reduction in NO_(x). In addition, the Hgconcentration at the baghouse outlet may be measured as below half thatin the furnace, indicating at least, if not greater that 40% mercuryremoval as a result of the pre-combustion additive.

As noted above, while embodiments of the invention have been describedin general terms of the combustion of carbonaceous fuel, all suchinventive principles are equally applicable to various gasificationprocess. For example, embodiments of the invention may include a methodof catalyzing the gasification of carbonaceous feedstock. Such processmay include, for example the steps of segregating a quantity ofparticulate matter source compound and/or calcium source compound. Thesesegregated constituents may be distributed across the surface area of acarbonaceous feedstock particulate forming a catalytically enhancedcarbonaceous feedstock. This catalytically enhanced carbonaceousfeedstock may be inserted into a gasifier system where its gasificationmay produce select product gas components having decreased contaminantscompared to gasification without said catalytically enhancedcarbonaceous feedstock. In other embodiments, gasification of acatalytically enhanced carbonaceous feedstock may result in increasedyield of select product gas components compared to gasification withoutsaid catalytically enhanced carbonaceous feedstock.

For example in a preferred embodiment, segregated particulate matter,such as segregated fly ash, and a segregated calcium source compound,such as segregated limestone may be distributed across the surface areaof a carbonaceous feedstock particulate forming a catalytically enhancedcarbonaceous feedstock. Gasification of such catalytically enhancedcarbonaceous feedstock may result in the reduction of NOx, SOx, mercuryand other gasification emissions compared to gasification of anon-treated carbonaceous feedstock. In a preferred embodimentsGasification of such catalytically enhanced carbonaceous feedstock mayresult in the reduction of NOx, and mercury emissions by at least orgreater than 20%.

Application of the current invention may be applicable to a variety ofgasification systems. For example, gasifying a catalytically enhancedcarbonaceous feedstock may include the steps of: gasifying saidcatalytically enhanced carbonaceous feedstock in at least one coalgasifier; gasifying said catalytically enhanced carbonaceous feedstockin at least one fixed bed gasifier; gasifying said catalyticallyenhanced carbonaceous feedstock in at least one downdraft co-currentcurrent fixed bed gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one updraft co-current current fixedbed gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one updraft counter-current fixed bed gasifier;gasifying said catalytically enhanced carbonaceous feedstock in at leastone cross-draft fixed bed gasifier; gasifying said catalyticallyenhanced carbonaceous feedstock in at least one open core fixed bedgasifier; gasifying said catalytically enhanced carbonaceous feedstockin at least one pressurized circulating gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one fluidizedbed gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one atmospheric circulating gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least onefluidized bed gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one hydrothermal gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least onesupercritical water gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one plasma arc gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least one2-stage gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one open-top gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one aqueousphase reforming gasifier; and gasifying said catalytically enhancedcarbonaceous feedstock in at least one partial oxidation gasifier.

Application of the current invention may be applicable to a variety ofgasification feedstock. Exemplary carbonaceous feedstock may include:coal; bitumous; anthracite; subbituminous; lignite; liquefied coal;petroleum coke; biomass; petroleum; peat; residual oils; natural gas;pulverized coal; waste-derived feedstocks; wood pellets; wood chips;waste wood; plastic; aluminum; municipal solid waste (MSW);refuse-derived fuel (RDF); agricultural and industrial waste; sewagesludge; switch grass; seed corn; corn stover; and crop residues.

Additional embodiments of the inventive technology may include increasesin the yield and/or rate of carbonaceous feedstock consumption resultingin perhaps improved yields of select product gas components and/orsyngas than gasification without said catalytically enhancedcarbonaceous feedstock. Yield increase may select product gas componentsand/or syngas may include, in some embodiments a yield increase ofapproximately 0.1-10% percent. Additional embodiments may include evenhigher select product gas components and/or syngas yield improvements.

Naturally, all embodiments discussed herein are merely illustrative andshould not be construed to limit the scope of the inventive technologyconsistent with the broader inventive principles disclosed. As may beeasily understood from the foregoing, the basic concepts of the presentinventive technology may be embodied in a variety of ways. It generallyinvolves systems, methods, techniques as well as devices to accomplishproviding methods and apparatus for the treatment of carbonaceous fueland the like. In this application, the improved carbonaceous fueltreatment techniques are disclosed as part of the results shown to beachieved by the various devices described and as steps which areinherent to utilization. They are simply the natural result of utilizingthe devices as intended and described. In addition, while some devicesare disclosed, it should be understood that these not only accomplishcertain methods but also can be varied in a number of ways. Importantly,as to all of the foregoing, all of these facets should be understood tobe encompassed by this disclosure.

While the invention has been described in connection with a preferredembodiment, it is not intended to limit the scope of the invention tothe particular form set forth, but on the contrary, it is intended tocover such alternatives, modifications, and equivalents as may beincluded within the spirit and scope of the invention as defined by thestatements of invention. As can be easily understood from the foregoing,the basic concepts of the present invention may be embodied in a varietyof ways. It involves both techniques as well as devices to accomplishthe appropriate system for providing for the treatment of carbonaceousfuel the like. In this application, the techniques are disclosed as partof the results shown to be achieved by the various devices described andas steps which are inherent to utilization. They are simply the naturalresult of utilizing the devices as intended and described. In addition,while some devices are disclosed, it should be understood that these notonly accomplish certain methods but also can be varied in a number ofways. Importantly, as to all of the foregoing, all of these facetsshould be understood to be encompassed by this disclosure.

The discussion included in this application is intended to serve as abasic description. The reader should be aware that the specificdiscussion may not explicitly describe all embodiments possible; manyalternatives are implicit. It also may not fully explain the genericnature of the invention and may not explicitly show how each feature orelement can actually be representative of a broader function or of agreat variety of alternative or equivalent elements. Again, these areimplicitly included in this disclosure. Where the invention is describedin method-oriented terminology, each element of the claims correspondsto a device. Apparatus claims may not only be included for the devicedescribed, but also method or process claims may be included to addressthe functions the invention and each element performs. Neither thedescription nor the terminology is intended to limit the scope of theclaims that will be included in any subsequent patent application.

It should also be understood that a variety of changes may be madewithout departing from the essence of the invention. Such changes arealso implicitly included in the description. They still fall within thescope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied upon when drafting anyclaims. It should be understood that such language changes and broaderor more detailed claiming may be accomplished at a later date (such asby any required deadline) or in the event the applicant subsequentlyseeks a patent filing based on this filing. With this understanding, thereader should be aware that this disclosure is to be understood tosupport any subsequently filed patent application that may seekexamination of as broad a base of claims as deemed within theapplicant's right and may be designed to yield a patent coveringnumerous aspects of the invention both independently and as an overallsystem.

Further, each of the various elements of the invention and claims mayalso be achieved in a variety of manners. Additionally, when used orimplied, an element is to be understood as encompassing individual aswell as plural structures that may or may not be physically connected.This disclosure should be understood to encompass each such variation,be it a variation of an embodiment of any apparatus embodiment, a methodor process embodiment, or even merely a variation of any element ofthese. Particularly, it should be understood that as the disclosurerelates to elements of the invention, the words for each element may beexpressed by equivalent apparatus terms or method terms—even if only thefunction or result is the same. Such equivalent, broader, or even moregeneric terms should be considered to be encompassed in the descriptionof each element or action. Such terms can be substituted where desiredto make explicit the implicitly broad coverage to which this inventionis entitled. As but one example, it should be understood that allactions may be expressed as a means for taking that action or as anelement which causes that action. Similarly, each physical elementdisclosed should be understood to encompass a disclosure of the actionwhich that physical element facilitates. Regarding this last aspect, asbut one example, the disclosure of a “pulverizer” should be understoodto encompass disclosure of the act of “pulverizing”—whether explicitlydiscussed or not—and, conversely, were there effectively disclosure ofthe act of “pulverizing”, such a disclosure should be understood toencompass disclosure of a “pulverizing method and/or technique, and ordevice” and even a “means for pulverizing.” Such changes and alternativeterms are to be understood to be explicitly included in the description.

Any patents, publications, or other references mentioned in thisapplication for patent, such as in the specification or an IDS arehereby incorporated herein by reference in their entirety. Any prioritycase(s) claimed by this application is hereby appended and herebyincorporated herein by reference in their entirety. In addition, as toeach term used it should be understood that unless its utilization inthis application is inconsistent with a broadly supportinginterpretation, common dictionary definitions should be understood asincorporated for each term and all definitions, alternative terms, andsynonyms such as contained in the Random House Webster's UnabridgedDictionary, second edition are hereby incorporated herein by referencein their entirety. Finally, all references listed in the list ofReferences To Be Incorporated By Reference In Accordance With The PatentApplication or other information disclosure statement and the like filedwith the application are hereby appended and hereby incorporated hereinby reference in their entirety, however, as to each of the above, to theextent that such information or statements incorporated by referencemight be considered inconsistent with the patenting of this/theseinvention(s) such statements are expressly not to be considered as madeby the applicant(s).

Thus, the applicant(s) should be understood to have support to claim andmake a statement of invention to at least: i) each of the system (withcorresponding methods and apparatus) of providing methods and/orapparatus for the treatment of carbonaceous fuel as herein disclosed anddescribed, ii) the related methods disclosed and described, iii)similar, equivalent, and even implicit variations of each of thesedevices and methods, iv) those alternative designs which accomplish eachof the functions shown as are disclosed and described, v) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, vi) each feature, component, and step shown as separate andindependent inventions, vii) the applications enhanced by the varioussystems or components disclosed, viii) the resulting products producedby such systems or components, ix) each system, method, and elementshown or described as now applied to any specific field or devicesmentioned, x) methods and apparatuses substantially as describedhereinbefore and with reference to any of the accompanying examples, xi)the various combinations and permutations of each of the elementsdisclosed, xii) each potentially dependent claim or concept as adependency on each and every one of the independent claims or conceptspresented, and xiii) all inventions described herein.

In addition and as to automated and/or computer aspects and each aspectamenable to programming or other electronic automation, the applicant(s)should be understood to have support to claim and make a statement ofinvention to at least: xvi) processes performed with the aid of or on acomputer and or controller as described throughout the above discussion,xv) a programmable apparatus as described throughout the abovediscussion, xvi) a computer readable memory encoded with data to directa computer comprising means or elements which function as describedthroughout the above discussion, xvii) a computer configured as hereindisclosed and described, xviii) individual or combined subroutines andprograms as herein disclosed and described, xix) the related methodsdisclosed and described, xx) similar, equivalent, and even implicitvariations of each of these systems and methods, xxi) those alternativedesigns which accomplish each of the functions shown as are disclosedand described, xxii) those alternative designs and methods whichaccomplish each of the functions shown as are implicit to accomplishthat which is disclosed and described, xxiii) each feature, component,and step shown as separate and independent inventions, and xxiv) thevarious combinations and permutations of each of the above.

With regard to claims whether now or later presented for examination, itshould be understood that for practical reasons and so as to avoid greatexpansion of the examination burden, the applicant may at any timepresent only initial claims or perhaps only initial claims with onlyinitial dependencies. The office and any third persons interested inpotential scope of this or subsequent applications should understandthat broader claims may be presented at a later date in this case, in acase claiming the benefit of this case, or in any continuation in spiteof any preliminary amendments, other amendments, claim language, orarguments presented, thus throughout the pendency of any case there isno intention to disclaim or surrender any potential subject matter. Itshould be understood that if or when broader claims are presented, suchmay require that any relevant prior art that may have been considered atany prior time may need to be re-visited since it is possible that tothe extent any amendments, claim language, or arguments presented inthis or any subsequent application are considered as made to avoid suchprior art, such reasons may be eliminated by later presented claims orthe like. Both the examiner and any person otherwise interested inexisting or later potential coverage, or considering if there has at anytime been any possibility of an indication of disclaimer or surrender ofpotential coverage, should be aware that no such surrender or disclaimeris ever intended or ever exists in this or any subsequent application.Limitations such as arose in Hakim v. Cannon Avent Group, PLC, 479 F.3d1313 (Fed. Cir 2007), or the like are expressly not intended in this orany subsequent related matter. In addition, support should be understoodto exist to the degree required under new matter laws—including but notlimited to European Patent Convention Article 123(2) and United StatesPatent Law 35 USC 132 or other such laws—to permit the addition of anyof the various dependencies or other elements presented under oneindependent claim or concept as dependencies or elements under any otherindependent claim or concept. In drafting any claims at any time whetherin this application or in any subsequent application, it should also beunderstood that the applicant has intended to capture as full and broada scope of coverage as legally available. To the extent thatinsubstantial substitutes are made, to the extent that the applicant didnot in fact draft any claim so as to literally encompass any particularembodiment, and to the extent otherwise applicable, the applicant shouldnot be understood to have in any way intended to or actuallyrelinquished such coverage as the applicant simply may not have beenable to anticipate all eventualities; one skilled in the art, should notbe reasonably expected to have drafted a claim that would have literallyencompassed such alternative embodiments.

Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.It should be understood that this application also provides support forany combination of elements in the claims and even incorporates anydesired proper antecedent basis for certain claim combinations such aswith combinations of method, apparatus, process, and the like claims.

Finally, any claims set forth at any time are hereby incorporated byreference as part of this description of the invention, and theapplicant expressly reserves the right to use all of or a portion ofsuch incorporated content of such claims as additional description tosupport any of or all of the claims or any element or component thereof,and the applicant further expressly reserves the right to move anyportion of or all of the incorporated content of such claims or anyelement or component thereof from the description into the claims orvice-versa as necessary to define the matter for which protection issought by this application or by any subsequent continuation, division,or continuation-in-part application thereof, or to obtain any benefitof, reduction in fees pursuant to, or to comply with the patent laws,rules, or regulations of any country or treaty, and such contentincorporated by reference shall survive during the entire pendency ofthis application including any subsequent continuation, division, orcontinuation-in-part application thereof or any reissue or extensionthereon. The inventive subject matter is to include, but certainly notbe limited as, a system substantially as herein described with referenceto any one or more of the Figures and Description (including thefollowing: for example, the process according to any claims and furthercomprising any of the steps as shown in any Figures, separately, in anycombination or permutation).

What is claimed is:
 1. A method of catalyzing the gasification ofcarbonaceous feedstock comprising the steps of: segregating a quantityof particulate matter source compound to an ultra-fine particle size;segregating a quantity of calcium source compound to an ultra-fineparticle size; milling at least one carbonaceous feedstock in thepresence of said segregated particulate matter source compound and saidsegregated calcium source compound to form a catalytically enhancedcarbonaceous feedstock; processing said catalytically enhancedcarbonaceous feedstock in a gasification reactor; and gasifying saidcatalytically enhanced carbonaceous feedstock to produce select productgas components wherein said step of gasification results in productionof select product gas components having catalytically decreasedcontaminants than gasification without said catalytically enhancedcarbonaceous feedstock.
 2. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 1 wherein said step ofmilling comprises the step of distributing said segregated particulatematter source compound and said segregated calcium source compoundacross the surface area of said carbonaceous feedstock.
 3. A method ofcatalyzing the gasification of carbonaceous feedstock as described inclaim 1 wherein said step of segregating a quantity of particulatematter source compound comprises a step selected from the groupconsisting of segregating a quantity of fly ash and segregating aquantity of particulate matter source compound from the combustion of acarbonaceous fuel.
 4. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 1 wherein said step ofsegregating a quantity of calcium source compound comprises the step ofsegregating a quantity of limestone source compound.
 5. A method ofcatalyzing the gasification of carbonaceous feedstock as described inclaim 1 and further comprising the step of partially combusting aportion of said catalytically enhanced carbonaceous feedstock.
 6. Amethod of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 1 wherein said step of gasification results incatalytically reducing formation of NOx emissions compared togasification without said catalytically enhanced carbonaceous feedstock.7. A method of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 1 wherein said step of gasification results incatalytically reducing formation of mercury emissions compared togasification without said catalytically enhanced carbonaceous feedstock.8. A method of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 1 wherein said step of gasification results incatalytically reducing formation of sulfur emissions compared togasification without said catalytically enhanced carbonaceous feedstock.9. A method of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 6 wherein said step of catalytically reducingformation of NOx emissions comprises the step of catalytically reducingformation of NOx emissions by at least 20% compared to gasificationwithout said catalytically enhanced carbonaceous feedstock.
 10. A methodof catalyzing the gasification of carbonaceous feedstock as described inclaim 8 wherein said step of catalytically reducing formation of sulfuremissions comprises the step of catalytically reducing hydrogen sulfideformation compared to gasification without said catalytically enhancedcarbonaceous feedstock.
 11. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 1 wherein said carbonaceousfeedstock comprises at least one carbonaceous feedstock selected fromthe group consisting of: coal; bitumous; anthracite; subbituminous;lignite; liquefied coal; petroleum coke; biomass; petroleum; peat;residual oils; natural gas; pulverized coal; waste-derived feedstocks;wood pellets; wood chips; waste wood; plastic; aluminum; municipal solidwaste (MSW); refuse-derived fuel (RDF); agricultural and industrialwaste; sewage sludge; switch grass; seed corn; corn stover; and cropresidues.
 12. A method of catalyzing the gasification of carbonaceousfeedstock as described in claim 1 wherein said select product gascomponents comprise at least one select product gas component selectedfrom the group consisting of: carbon monoxide; hydrogen gas; carbondioxide; and/or methane.
 13. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 1 wherein said step ofgasifying said catalytically enhanced carbonaceous feedstock comprisesthe step of gasifying said catalytically enhanced carbonaceous feedstockselected from the group consisting of: gasifying said catalyticallyenhanced carbonaceous feedstock in at least one coal gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least one fixedbed gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one downdraft co-current current fixed bedgasifier; gasifying said catalytically enhanced carbonaceous feedstockin at least one updraft co-current current fixed bed gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least oneupdraft counter-current fixed bed gasifier; gasifying said catalyticallyenhanced carbonaceous feedstock in at least one cross-draft fixed bedgasifier; gasifying said catalytically enhanced carbonaceous feedstockin at least one open core fixed bed gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least onepressurized circulating gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one fluidized bed gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least oneatmospheric circulating gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one fluidized bed gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least onehydrothermal gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one supercritical water gasifier;gasifying said catalytically enhanced carbonaceous feedstock in at leastone plasma arc gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one 2-stage gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one open-topgasifier; gasifying said catalytically enhanced carbonaceous feedstockin at least one aqueous phase reforming gasifier; and gasifying saidcatalytically enhanced carbonaceous feedstock in at least one partialoxidation gasifier.
 14. A method of catalyzing the gasification ofcarbonaceous feedstock comprising the steps of: segregating a quantityof particulate matter source compound to an ultra-fine particle size;segregating a quantity of calcium source compound to an ultra-fineparticle size; milling at least one carbonaceous feedstock in thepresence of said segregated particulate matter source compound and saidsegregated calcium source compound to form a catalytically enhancedcarbonaceous feedstock; processing said catalytically enhancedcarbonaceous feedstock in a gasification reactor; and gasifying saidcatalytically enhanced carbonaceous feedstock wherein said step ofgasification results in catalytically increased yield of select productgas components than gasification without said catalytically enhancedcarbonaceous feedstock.
 15. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 14 wherein said step ofmilling comprises the step of distributing said segregated particulatematter source compound and said segregated calcium source compoundacross the surface area of said carbonaceous feedstock.
 16. A method ofcatalyzing the gasification of carbonaceous feedstock as described inclaim 14 wherein said step of segregating a quantity of particulatematter source compound comprises a step selected from the groupconsisting of segregating a quantity of fly ash and segregating aquantity of particulate matter source compound from the combustion of afirst carbonaceous fuel.
 17. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 14 wherein said step ofsegregating a quantity of calcium source compound comprises the step ofsegregating a quantity of limestone source compound.
 18. A method ofcatalyzing the gasification of carbonaceous feedstock as described inclaim 14 and further comprising the step of partially combusting aportion of said catalytically enhanced carbonaceous feedstock.
 19. Amethod of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 14 wherein said carbonaceous feedstock comprises atleast one carbonaceous feedstock selected from the group consisting of:liquid carbonaceous feedstock, solid carbonaceous feedstock, gascarbonaceous feedstock.
 20. A method of catalyzing the gasification ofcarbonaceous feedstock as described in claim 14 wherein saidcarbonaceous feedstock comprises at least one carbonaceous feedstockselected from the group consisting of: coal; bitumous; anthracite;subbituminous; lignite; liquefied coal; petroleum coke; biomass;petroleum; peat; residual oils; natural gas; pulverized coal;waste-derived feedstocks; wood pellets; wood chips; waste wood; plastic;aluminum; municipal solid waste (MSW); refuse-derived fuel (RDF);agricultural and industrial waste; sewage sludge; switch grass; seedcorn; corn stover; and crop residues.
 21. A method of catalyzing thegasification of carbonaceous feedstock as described in claim 14 whereinsaid select product gas components comprise syngas.
 22. A method ofcatalyzing the gasification of carbonaceous feedstock as described inclaim 14 wherein said select product gas components comprise at leastone select product gas component selected from the group consisting of:carbon monoxide; hydrogen gas; carbon dioxide; and methane.
 23. A methodof catalyzing the gasification of carbonaceous feedstock as described inclaim 14 wherein said step of gasifying comprises the step ofcatalytically improving shift reactions during gasification.
 24. Amethod of catalyzing the gasification of carbonaceous feedstock asdescribed in claim 14 wherein said step of gasifying comprises the stepof catalytically improving the reaction of char and oxygen to formcarbon monoxide and/or carbon dioxide.
 25. A method of catalyzing thegasification of carbonaceous feedstock as described in claim 14 whereinsaid step of gasifying comprises the step of catalytically improving thereaction of carbon and water to form carbon monoxide and/or hydrogengas.
 26. A method of catalyzing the gasification of carbonaceousfeedstock as described in claim 14 wherein said step of gasifyingcomprises the step of catalytically improving the rate of carbonaceousfeedstock conversion to select product gas components thereby increasingthe yield of select product gas components compared to gasificationwithout said catalytically enhanced carbonaceous feedstock.
 27. A methodof catalyzing the gasification of carbonaceous feedstock as described inclaim 14 wherein said step of gasifying comprises the step ofcatalytically improving carbonaceous feedstock consumption.
 28. A methodof catalyzing the gasification of carbonaceous feedstock as described inclaim 14 wherein said step of gasifying said catalytically enhancedcarbonaceous feedstock comprises the step of gasifying saidcatalytically enhanced carbonaceous feedstock selected from the groupconsisting of: gasifying said catalytically enhanced carbonaceousfeedstock in at least one coal gasifier; gasifying said catalyticallyenhanced carbonaceous feedstock in at least one fixed bed gasifier;gasifying said catalytically enhanced carbonaceous feedstock in at leastone downdraft co-current current fixed bed gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one updraftco-current current fixed bed gasifier; gasifying said catalyticallyenhanced carbonaceous feedstock in at least one updraft counter-currentfixed bed gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one cross-draft fixed bed gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one open corefixed bed gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one pressurized circulating gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least onefluidized bed gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one atmospheric circulating gasifier;gasifying said catalytically enhanced carbonaceous feedstock in at leastone fluidized bed gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one hydrothermal gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least onesupercritical water gasifier; gasifying said catalytically enhancedcarbonaceous feedstock in at least one plasma arc gasifier; gasifyingsaid catalytically enhanced carbonaceous feedstock in at least one2-stage gasifier; gasifying said catalytically enhanced carbonaceousfeedstock in at least one open-top gasifier; gasifying saidcatalytically enhanced carbonaceous feedstock in at least one aqueousphase reforming gasifier; and gasifying said catalytically enhancedcarbonaceous feedstock in at least one partial oxidation gasifier.
 29. Amethod of generating a catalytically enhanced carbonaceous feedstockcomprising the steps of: capturing a quantity of particulate mattersource compound from the combustion of a carbonaceous fuel; segregatingsaid quantity of said captured particulate matter source compound to anultra-fine particle size; establishing a quantity of calcium sourcecompound; segregating said quantity of calcium source compound to anultra-fine particle size; milling at least one carbonaceous feedstock inthe presence of said segregated particulate matter source compound andsaid segregated calcium source compound to form a catalytically enhancedcarbonaceous feedstock.